JP2994760B2 - Hydrazine derivatives - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention is directed to novel hydrazine derivatives that exhibit activity as acaricides and nematicides. The present invention also provides
Acaricidal and nematicidal compositions containing such hydrazine derivatives are intended.

BACKGROUND OF THE INVENTION The destruction of crops by nematodes and mites has given serious problems to agriculture. Soybeans, corn, peanuts,
A wide variety of field crops, including valuable crops such as cotton, alfalfa and tobacco, require protection from nematodes and mites. In addition, vegetables such as tomato, potato, sugar beet, carrot,
Also fruits, nuts, ornamental plants and nursery crops such as apples, peaches, pears, citrus fruits and grapes will need to be protected from destruction by such pests. Particularly difficult-to-control types of insects are those that live in the ground at one or more stages of their lives and cause damage to the roots of agriculturally valuable plants. For this reason, the development of new and more effective nematicides represents a continuing scientific activity. More specifically, there has been interest in developing acaricides that are effective as both ovicidal and larvicidal agents.

In Chemical Abstracts 108 (19): 163280d,
Certain alkyl phenyl hydrazine carboxylates and their synthesis and use in miticides are described. U.S. Pat. No. 4,725,302 describes certain substituted phenylhydrazines and phenyloxadiazolinones and their use in pesticides. European Patent 0674
No. 71 describes certain 7-substituted 2,3-dihydrobenzofurans, their synthesis and their use as pesticides or chemical intermediates. Derwent
ent). Abstract 88-312695 / 44 describes certain arylhydrazides of trifluoroacetic acid as having fungicidal, fungicidal, acaricidal and antiseptic activity.
U.S. Pat. No. 5,367,093 describes certain insecticidal phenylhydrazine derivatives.

It is an object of the present invention to provide novel hydrazine derivatives useful as acaricides and nematicides.

SUMMARY OF THE INVENTION Or Here, R is C ₁ -C ₆ alkoxy or C ₁ -C ₆ alkyl, and R ^{1 is} unsubstituted or C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkyl,
C ₁ -C ₄ alkylthio, halogen, fluorenyl substituted by one or more substituents selected from C ₁ -C ₄ haloalkyl and nitro, thienyl, pyridyl or thiazolyl, R ² is C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, C ₃ −
Which is C ₆ cycloalkyl, C ₁ -C ₆ haloalkyl, C ₂ -C ₆ alkenyl, C ₁ -C ₆ alkylthio or C ₂ -C ₆ alkoxyalkyl.

The compounds of formulas (I) and (II) and compositions containing these compounds are useful as acaricides and nematicides.

DETAILED DESCRIPTION OF THE INVENTION Preferred of the compounds of formulas (I) and (II) are R
Is C ₁ -C ₄ alkoxy or C ₁ -C ₄ alkyl, R ¹ is fluorenyl, thienyl, pyridyl or thiazolyl unsubstituted or substituted by one or more C ₁ -C ₄ alkyl, and R ² is ₁ -C is a compound which is ₄ alkyl or C ₁ -C ₄ alkoxy. Of the compounds of formulas (I) and (II), more preferred is where R is methoxy or methyl and R ¹ is 2
-Methyl-4-thiazolyl, 2-pyridinyl, 2-thienyl, 3-pyridinyl or 9H-fluoren-3-yl, wherein R ² is 1-methylethyl.

The compounds of the present invention have the formula Wherein R and R ¹ are as described above, also by reacting an intermediate hydrazine derivative of the formula with an acyl halide of the formula ClCO ₂ R ² where R ² is as described above. can do.

The intermediate hydrazine derivative can be synthesized by diazotizing the corresponding aniline with sodium nitrite and then reducing with stannous chloride.

The pesticidal composition of the present invention comprises (a) the above-mentioned formula (I)
Alternatively, it comprises a compound having a structure within the structure of (II) and (b) a suitable carrier. Such a suitable carrier is
It may be a solid or liquid in nature.

Suitable liquid carriers include water, alcohols, ketones, phenols, toluene and xylenes. In such formulations, additives conventionally used in the art, such as one or more surfactants and / or non-active agents, may be used to facilitate the handling and application of the resulting pesticidal composition. Active diluents can be used.

Alternatively, the pesticidal composition may contain a solid carrier in the form of a powder, granule, wettable powder, paste, aerosol, emulsion, emulsifiable concentrate, and water-soluble solid.

For example, the pesticidal compounds of the present invention can be applied as dusts when mixed with or absorbed by powdered solid carriers, such as mineral silicates (eg, mica, talc, fluorite and clay). If this is combined with a surfactant, a wettable powder is obtained, which is applied directly to the place to be treated. Alternatively, a powdered solid carrier incorporating the compound may be dispersed in water to form a suspension for application as is.

Granular preparations of the present compounds are suitable for field treatment and are suitable for application by general application, side dressing, soil incorporation or seed treatment, granulated or pelletized carriers such as granular clay, hillstone Produced as appropriate using charcoal or corn cobs.

Alternatively, the pesticidal compound, when used in a liquid carrier, is dispersed as a solution in a compatible solvent such as acetone, benzene, toluene or kerosene, or dispersed in a suitable non-solvent medium such as water. When used as a liquid, it can be applied as a liquid or spray. Another method of application to the area to be treated is aerosol treatment, in which the compound is dissolved in an aerosol carrier which is liquid under pressure but is a gas at ambient temperature (eg 20 ° C) and atmospheric pressure at atmospheric pressure. I just need. Aerosol formulations can also be prepared by first dissolving the compound in a less volatile solvent and then mixing the resulting solution with a highly volatile liquid aerosol carrier.

For the pesticidal treatment of plants (this term encompasses plant parts), the compounds of the present invention may be treated with aqueous dispersants containing surfactant dispersants, which may be non-ionic, cationic or anionic. It is preferably applied as an emulsion. Suitable surfactants are known in the art and include, for example, those disclosed in US Pat. No. 2,547,724 (columns 3 and 4). The compound of the present invention is mixed with such a surfactant dispersant with or without an organic solvent to form a concentrate, and then water is added to the concentrate to obtain an aqueous suspension of the compound of the present invention at a desired concentration level. You can make a system.

In addition, the present compounds can be used with carriers that themselves have pesticidal activity, for example, insecticides, acaricides, fungicides or fungicides.

The amount of the pesticidally active compound in a given formulation depends on the particular pest to be controlled, the specific chemical composition and dosage form of the compound used, the method of application of the compound / formulation and the location of treatment. It will be appreciated that the pesticidally effective amount of the compound can vary widely, and therefore can vary widely.
However, in general, the concentration of the compound as the active ingredient in the pesticidal formulation can range from about 0.1 to about 95% by weight. Spray diluents may be as low as a few ppm, while in the extreme case, it may be useful to apply the highest concentration concentrate of the compound by ultra-trace techniques. Where plants make up the site of treatment, concentrations per unit area can range from about 0.01 to about 50 pounds / acre, and for crops such as corn, tobacco, rice, etc., about 0.1 to about 10 pounds / acre. Concentrations can be used.

To control pests, the compound can be sprayed directly on the pest and / or on the plants where the pest is feeding or nesting. The pest control formulation may also be applied to soil or other media in which the pest is present.

Harmful nematodes and mites attack a wide variety of plants, including both ornamental and agricultural plants, eat roots and / or leaves, absorb life-supporting fluids from plants, and remove toxins. Harms by secreting and often transmitting disease. The compounds of the present invention can be advantageously used to minimize or prevent such harm. The particular application and the choice and concentration of these compounds will, of course, vary with circumstances, such as geographic region, climate, terrain, plant tolerance, and the like. For a particular situation, one of ordinary skill in the art can readily determine appropriate compounds, concentrations and applications by performing routine experimentation.

The compounds of the present invention are particularly useful as nematicides and acaricides for foliar and / or soil applications.

The following examples are provided merely to illustrate the scope of the present invention.

Example 1 Preparation of 1-methylethyl 2- [2-methoxy-5- (2-methyl-4-thiazolyl) phenyl] hydrazinecarboxylate (Compound 1) 2.5 g of 2-methoxy-5- (2-methyl-4 -Thiazolyl) aniline was added with 100 ml of water and 50 ml of concentrated hydrochloric acid, and the resulting mixture was stirred at -5 ° C. Next, the temperature was lowered to -5.
A solution of 1 g of sodium nitrite in 10 ml of water was added dropwise while maintaining the temperature. After addition of the aqueous sodium nitrite solution, the mixture was stirred at -5 ° C for 1 hour. Next, a solution of 10 g of stannous chloride in 20 ml of concentrated hydrochloric acid was quickly added to the mixture, followed by stirring for 1 hour, neutralization with sodium hydroxide, and extraction with dichloromethane. Evaporation of the dichloromethane yielded 1.5 g of the intermediate, 2-methoxy-5- (2-methyl-4-thiazolyl) phenylhydrazine, as an oil which was dissolved in 100 ml of toluene.

To the intermediate / toluene solution was added 1 g of pyridine, then 5 ml of 1-methylethyl chloroformate solution (1M in toluene) was added dropwise. After stirring for 1 hour, the mixture was washed with water and evaporated to dryness. The solid was washed well with hexane to give 1.5 g of 1-methylethyl 2-
[2-methoxy-5- (2-methyl-4-thiazolyl)
Phenyl] hydrazinecarboxylate (melting point 127-130
° C) remained.

Example 2 Preparation of 1-methylethyl [2-methoxy-5- (2-methyl-4-thiazolyl) phenyl] diazencarboxylate (compound 9) 1-methylethyl 2- [2-methoxy-5- of Example 1
To (1.5 g of (2-methyl-4-thiazolyl) phenyl] hydrazinecarboxylate was added 100 ml of toluene and 0.5 g of palladium (10% on carbon). The mixture was stirred vigorously at room temperature overnight, then filtered and the toluene was evaporated under reduced pressure. The product obtained as a red oil is 1.
2 g of 1-methylethyl [2-methoxy-5- (2-methyl-4-thiazolyl) phenyl] diazencarboxylate.

The compounds summarized in Tables 1 and 2 were prepared using the procedures described above. Each of the compounds thus prepared is characterized by proton NMR properties.

Compounds 1-8 were made from the intermediate compounds identified below.

Example 3 Preparation of Compositions The following examples relate to the use of the compounds of the present invention as pesticides. All stock solutions of compounds in these examples were prepared by dissolving 0.3 g of each test compound in 10 ml of acetone and dissolving in distilled water.
It was adjusted to 3000 ppm by adding 90 ml and 4 drops of ethoxylated sorbitan monolaurate, or a similar suitable wetting agent. This stock solution was used for each of the following examples, and the dilution was performed as described.

All tests discussed below involve treatment with compounds of the present invention at concentrations of 500 and 40 ppm, always with a control without active compound, to allow comparisons on which to calculate percent control. It was repeated.

Example 4 Tick adult and tick ovicidal / larvicide test One day before treatment, a tree tanglefoot in the form of the number "8" is attached to each of the two primary leaves of cowpea. (One from each of the two plants in one pot). The circle closer to the stem of each figure eight was designated for the tick oocyte / larvicide test, and the circles farther from the stem were designated for the tick adultericide test.

Groups of adult mites (Tetranychus urticae Koch) were transferred into oocyte test circles one day prior to treatment and females laid eggs up to one hour before treatment (all ticks were removed during treatment). 100 diluted from 3000 ppm stock solution to plants
The 0 ppm solution was sprayed down.

One day after treatment, a group of approximately 25 adult ticks was transferred into a ring for an insecticide test. Five days later, these rings were examined for live mites remaining on the leaves. Percent control was calculated based on the number of mites that survived the plants examined.

Nine days after treatment, the rings for the ovicidal / larvicidal test were examined for hatched eggs and live immature mites. Percent control was calculated based on the number of embryonated eggs and live immature mites on the plant. When the treatment effect was an effect on eggs, the control was called ovicidal (O), and when the treatment effect was an effect on immature insects, the control was called larvicidal (L).

Table 3 shows the results of the tick adult insecticide (MI) test and the ovicidal / larvicide (MIOVL) test.

Example 5 Nematode test 3000 ppm stock solution was diluted to 1000 ppm. 25 per compound
ml of the root of the root-knot nematode (Meloidogyne incognita) on a 500g pot of soil mixed with eggs
l concentration, sc).

One day after treatment, each pot was planted with two tomato seedlings.
Nineteen days after planting the seedlings, their roots were evaluated for knots and galls, and the percent control based on the level of damage in the plants.

 Table 3 shows the results of the nematode test (NE).

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI C07D 333/20 C07D 333/20 (72) Inventor Decayer, Mark Achille Canada N2K 1W3 Ontario, Waterloo, Box Berry Drive 333 (72) Inventor McPhee, Derek James Canada 1 2 5 On Tario, Guelph, Edinburgh Road S. 457, Apartment 506 (72) Inventor MacDonald, Paul Thomas United States 06762 Milley Dam Road, Middlebury, CT 43 (56) References JP-A-2-152922 (JP, A) JP-A-63-267752 (JP, A) JP-A-62-238258 (JP, A) JP-A-53-149941 (JP, A) JP-A-7-502267 (JP, A) US Patent 3,755,551 (US, A) Agric. Food. Chem. , 42 [6] (1994), 1358-1360 (58) Fields investigated (Int. Cl. ⁶ , DB name) C07C 243/28 C07C 245/06 C07D 213/42 C07D 277/28 C07D 333/20 A01N 47 / 24 CAPLUS (STN) REGISTRY (STN) WPIDS (STN)

Claims (20)

(57) [Claims] (1) Expression Or Where R is C ₁ -C ₆ alkoxy or C ₁ -C ₆ alkyl, R ¹ is unsubstituted or C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkylthio, halogen, Fluorenyl, thienyl, pyridyl or thiazolyl substituted by one or more substituents selected from C ₁ -C ₄ haloalkyl and nitro, wherein R ² is C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy,
A compound having the formula: C ₃ -C ₆ cycloalkyl, C ₁ -C ₆ haloalkyl, C ₂ -C ₆ alkenyl, C ₁ -C ₆ alkylthio or C ₂ -C ₆ alkoxyalkyl. 2. The compound according to claim 1, wherein R is C ₁ -C ₄ alkoxy or C ₁ -C ₄ alkyl. 3. The method of claim 2, wherein R is methoxy or methyl.
A compound as described. 4. The compound according to claim 1, wherein R ¹ is fluorenyl, thienyl, pyridyl or thiazolyl, unsubstituted or substituted by one or more C ₁ -C ₄ alkyl. 5. The compound according to claim 4, wherein R ¹ is 2-methyl-4-thiazolyl, 2-pyridinyl, 2-thienyl, 3-pyridinyl or 9H-fluoren-3-yl. 6. The compound according to claim 1, wherein R ² is C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy. 7. The compound according to claim 6, wherein R ² is 1-methylethyl. 8. A fluorenyl, thienyl, pyridyl or thiazolyl, wherein R is C ₁ -C ₄ alkoxy or C ₁ -C ₄ alkyl and R ¹ is unsubstituted or substituted by one or more C ₁ -C ₄ alkyl. The compound of claim ₁ , wherein R ² is C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy. 9. R is methoxy or methyl, and R ¹ is 2-
Methyl-4-thiazolyl, 2-pyridinyl, 2-thienyl, 3-pyridinyl or 9H- fluoren-3-yl, R ² is 1-methylethyl, compounds of claim 8. 10. The expression Wherein the R, R ¹ and R ² are as defined in claim 1, having the formula: 11. An expression Wherein the R, R ¹ and R ² are as defined in claim 1, having the formula: 12. The expression Where R is C ₁ -C ₆ alkoxy or C ₁ -C ₆ alkyl, R ¹ is unsubstituted or C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkyl, halogen, C ₁ -C ₄ haloalkyl and An intermediate hydrazine compound having the formula: fluorenyl, thienyl, pyridyl or thiazolyl substituted by one or more substituents selected from nitro. 13. A fluorenyl, thienyl, pyridyl or thiazolyl group wherein R is C ₁ -C ₄ alkoxy or C ₁ -C ₄ alkyl and R ¹ is unsubstituted or substituted by one or more C ₁ -C ₄ alkyl. 11. The intermediate hydrazine compound of claim 10. 14. R is methoxy or methyl, and R ¹ is 2
12. The intermediate hydrazine compound according to claim 11, which is -methyl-4-thiazolyl, 2-pyridinyl, 2-thienyl, 3-pyridinyl or 9H-fluoren-3-yl. 15. An acaricidal composition comprising an acaricidal effective amount of the compound of claim 1 and an acceptable carrier. 16. A miticidal composition comprising a miticidally effective amount of a compound according to claim 8 and an acceptable carrier. 17. An acaricidal composition comprising a miticidally effective amount of a compound according to claim 9 and an acceptable carrier. 18. A method for controlling harmful mites, comprising applying an acaricidal effective amount of the compound according to claim 1 to a place to be protected. 19. A method for controlling harmful mites, comprising applying an acaricidally effective amount of the compound according to claim 8 to a place to be protected. 20. A method for controlling harmful mites, comprising applying an acaricidal amount of the compound according to claim 9 to a place to be protected.